EP2323461A1 - Mikrowellenbestrahlungsgerät, verbundenes mikrowellenbestrahlungsgerät und verfahren zur herstellung eines glycobestandteils aus pflanzenmaterial - Google Patents

Mikrowellenbestrahlungsgerät, verbundenes mikrowellenbestrahlungsgerät und verfahren zur herstellung eines glycobestandteils aus pflanzenmaterial Download PDF

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Publication number
EP2323461A1
EP2323461A1 EP09802939A EP09802939A EP2323461A1 EP 2323461 A1 EP2323461 A1 EP 2323461A1 EP 09802939 A EP09802939 A EP 09802939A EP 09802939 A EP09802939 A EP 09802939A EP 2323461 A1 EP2323461 A1 EP 2323461A1
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EP
European Patent Office
Prior art keywords
microwave
plant material
glycocomponent
microwave radiating
aforementioned
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09802939A
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English (en)
French (fr)
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EP2323461B1 (de
EP2323461A4 (de
Inventor
Takashi Watanabe
Naoki Shinohara
Tomohiko Mitani
Masafumi OYADOMARI
Yasunori OHASHI
Pradeep Verma
Takahiko Tsumiya
Hisayuki SEGO
Yasuhiro Takami
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Japan Chemical Engineering and Machinery Co Ltd
Kyoto University NUC
Original Assignee
Japan Chemical Engineering and Machinery Co Ltd
Kyoto University NUC
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Publication of EP2323461A1 publication Critical patent/EP2323461A1/de
Publication of EP2323461A4 publication Critical patent/EP2323461A4/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/126—Microwaves
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/18—Purification of sugar juices by electrical means
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
    • C13K1/04—Purifying
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B6/00—Heating by electric, magnetic or electromagnetic fields
    • H05B6/64—Heating using microwaves
    • H05B6/70—Feed lines
    • H05B6/701—Feed lines using microwave applicators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/12—Processes employing electromagnetic waves
    • B01J2219/1203—Incoherent waves
    • B01J2219/1206—Microwaves
    • B01J2219/1248—Features relating to the microwave cavity
    • B01J2219/1269—Microwave guides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/12—Processes employing electromagnetic waves
    • B01J2219/1203—Incoherent waves
    • B01J2219/1206—Microwaves
    • B01J2219/1275—Controlling the microwave irradiation variables
    • B01J2219/1278—Time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/12—Processes employing electromagnetic waves
    • B01J2219/1203—Incoherent waves
    • B01J2219/1206—Microwaves
    • B01J2219/1275—Controlling the microwave irradiation variables
    • B01J2219/1281—Frequency

Definitions

  • the present invention is related to a microwave radiating device which may treat large amount of radiated material by irradiation of microwave; also related to a connecting type microwave radiating device which is a combination of the microwave radiating devices. Further, the present invention is related to a method which is able to produce glycocomponent efficiently as well as preventing over-decomposition of saccharides at a condition of low environmental impact, and is able to get polysaccharides by sufficient saccharification even at small amount enzyme.
  • microwave treatment provides extensive uses such as heating, sterilization, dehydration, extraction, or organic synthesis of materials at the field of organic chemistry or inorganic chemistry, biochemistry etc.
  • FIG. 5 A traditional microwave radiating device which is used presently is showing in FIG. 5 (refer to Pattern document 1).
  • the radiated material is firstly carried to a reacting tube 404 which is made of dielectric material such as ceramic, by a pump 402.
  • Microwave is generated by microwave radiating source 406, and passes through inner side of a waveguide 408 and reaches a heating device 410 which is set around the peripheral of the reacting tube 404.
  • the microwave penetrates the dielectric material, and the radiated material at inner side of the reacting tube 404 is subjected to the irradiation of microwave.
  • the radiated material is irradiated homogeneously.
  • the structure of a traditional microwave radiating device is complicated, so the periodical maintenance becomes great burden. Especially, to exchange the dielectric material used for penetration of microwave takes much time and costs a lot. Furthermore, the microwave radiating device is out of use during the maintenance time, then the proceeding of work is broken off.
  • the tube used in the microwave radiating device is made of dielectric material, the above problem can not be solved because there is an upper limit set on reacting temperature and pressure. Therefore it is desired to provide a microwave radiating device which is able to perform the reaction under the severe condition such as high temperature or pressure, decompression, vacuum etc., and able to dissolve the maintenance problem mentioned above.
  • the microwave radiating devices illustrating in Pattern document 2 and Pattern document 3 have dielectric material used in microwave penetrating portion. If the above portion of the microwave radiating device is out of order, the fixation would be very difficult because the device has to be dismantled. Moreover, the reacting container and the waveguide are manufactured as a unity, it is not easy to change penetration of microwave, e.g. it may not correspond to user's desire when a user hopes to change penetration of microwave to optimize the reaction condition.
  • the objects of the present invention are to provide a microwave radiating device, which realizes microwave treatment at severe condition of high temperature or pressure, decompression, vacuum etc., and to provide a microwave radiating device flexibly and rapidly corresponding to user's various needs such as short maintenance time, optimization of microwave penetration, addition of more microwave radiating device etc..
  • the present invention provides a method of producing glycocomponent from plant materials, wherein the method is able to produce glycocomponent efficiently as well as preventing over-decomposition of saccharides at a condition of low environmental impact, and is able to obtain polysaccharides by sufficient saccharification even at small amount of enzyme; and the present invention provides a method of producing glycocomponent from plant materials, wherein the method is able to produce glycocomponent efficiently as well as preventing over-decomposition of saccharides at a condition of low environmental impact, and is able to use water as dispersion medium, and is able to obtain polysaccharides by sufficient saccharification even at small amount of enzyme.
  • the microwave radiating device of the present invention is equipped with irradiating means which has microwave radiating source, and containers which accept radiated material inside.
  • the container has supply means which provides radiated material to container, and discharge means which discharges radiated material from container, and microwave receiving section which makes microwave irradiated from radiating means penetrate into the container through the medium of dielectric material.
  • microwave radiating device of the present invention is favorable that dielectric material and sheet shaped parts are laminated at the opening direction of microwave receiving section of the container.
  • the microwave radiating device of the present invention is favorable that the above dielectric material is sandwiched by at least 2 pieces of sheet shaped parts.
  • the microwave radiating device of the present invention may comprise dielectric materials which are selected one or more than two from the groups consist of quartz glass, fluorocarbon polymers, ceramics, alumina, sapphire, and diamond; and/or non-dielectric materials which are selected one or more than two from the groups consist of stainless, aluminium, titanium, nickel, gold, and silver.
  • the connecting type microwave radiating device of the present invention may be a combination device that combines more than two of the microwave radiating devices of the present invention.
  • a removable structure between a discharge means of one microwave radiating device of the above more than two of the microwave radiating devices and a supply means of the neighboring one microwave radiating device of the above more than two of the microwave radiating devices is able to attach to or remove from each other.
  • various containers of microwave radiating devices configure as a unity and form a flow way of radiated material.
  • the method of producing glycocomponent from plant material is able to produce glycocomponent efficiently as well as preventing over-decomposition of saccharides by comprising a separation process wherein a mixture of decomposed products of lignin and glycocomponent which at least contains solid-state polysaccharides is obtained by means of irradiating microwave under the existence of Lewis acid catalyst to a plant material which at least has lignocellulose.
  • the obtained glycocomponent here may be saccharized sufficiently even at small amount of enzyme.
  • microwave in the separation process 2000 MHz - 6000 MHz microwave is used. Further according to another method microwave irradiates 1 minute - 60 minutes. Further according to another method the plant material is heated to 80°C - 240°C when microwave irradiates. According to these conditions it is able to produce glycocomponent more efficiently.
  • the Lewis acid catalyst in the separation process may be selected at least one from the groups consist of aluminium chloride, aluminium bromide, aluminium sulfate, iron(III) chloride, zinc chloride, zinc bromide, and zinc sulfate.
  • the method of producing glycocomponent from plant material is able to produce glycocomponent efficiently as well as inhibiting over-decomposition of saccharides by comprising a separation process wherein obtaining a mixture of decomposed products of lignin and glycocomponent which at least contains solid-state polysaccharides by means of irradiating microwave to a plant material which at least has lignocellulose at the existence of molybdic acid ion, ammonium ion, and peroxides.
  • the obtained glycocomponent here may be saccharized sufficiently even at small amount of enzyme.
  • microwave in the separation process 2000 MHz - 6000 MHz microwave is used. Further in another method microwave irradiates 1 minute - 60 minutes. Further in another method the plant material is heated to 50°C - 240°C when microwave irradiates. According to these conditions it is able to produce glycocomponent more efficiently.
  • microwave irradiates at the state of dispersing plant material in water.
  • the time, trouble, or cost of posterior treatment would be decreased, also the environmental impact would be reduced.
  • the microwave radiating device of the present invention has at least one layer made of non-dielectric material, and located between atmosphere of inner side and outer side of the container where the reaction occurs; the layer may prevent microwave from escaping to outer atmosphere. Further, there is provided broader usage than traditional microwave radiating device because the microwave radiating device of the present invention is able to react at severe condition such as high temperature or pressure, decompression, vacuum etc.. Especially in the condition of carrying radiated material under pressure; the microwave radiating device of the present invention will still endure the high pressure which occurs inside of the reacting tube of the device. Further, the maintenance of microwave receiving section which has dielectric material is able to accomplish easily and rapidly by removing the irradiating means from the container.
  • the receiving section of the microwave radiating device of the present invention is comprised by lamination of dielectric material and sheet shaped parts, manufacturing is easier comparing to integrated microwave receiving section. Further, modification of the penetration amount on the radiated material is easy by adjusting the penetration of the sheet shaped parts. Further, if sheet shaped parts with various properties are prepared previously it is able to optimize the reaction condition by only exchange the sheet shaped parts, thus user's demand is able to correspond flexibly. The exchange of the sheet shaped parts is able to accomplish easily and rapidly by removing the irradiating means from the container.
  • the microwave radiating device of the present invention has at least more than two pieces of sheet shaped parts so it is possible to adjust penetration of microwave precisely. Further, during the time of removing the irradiating means and the container, the above dielectric materials are hardly damaged because the dielectric materials are sandwiched by sheet shaped parts.
  • the connecting type microwave radiating device of the present invention is able to provide devices to meet various user's needs. Especially when a user who is using the microwave radiating device of the present invention wants to increase treatment amount of microwave, he just purchases necessary microwave radiating devices and connects them without changing the whole device. Thus it is extremely economic. Further, each device is connected in removable state; at the time of maintenance just take the old device away and replace a new one, then connect again; the whole device is able to use continuously.
  • the method of producing glycocomponent from plant material according to the present invention is able to separate glycocomponent at a lower reaction temperature than that of traditional method, thus may efficiently produce glycocomponent which contains solid-state polysaccharides as well as inhibit over-decomposition of saccharides. Such inhibition of over-decomposition will reduce formation of furfural which impedes fermentation. Further, producing of glycocomponent according to the present invention is able to decrease cost and reduce environmental impact because the reaction will proceed at lower temperature than that of traditional method and even the enzyme is small quantity. Particularly, compare to the traditional method the present invention is able to conduct efficiently the producing of glycocomponent from plant material of conifer source.
  • the decomposed products of lignin obtained from the process of producing glycocomponent according to the present invention may be used in production of useful chemical substances such as aromatic compounds etc..
  • the amounts, types of the decomposed products of lignin according to the present invention are more than those of the traditional methods, and are suitable for production of chemical substances.
  • the produced glycocomponent according to the present invention may contain low molecule saccharides such as monosaccharide or oligosaccharide etc. in addition to solid-state polysaccharides. Such low molecule saccharides are able to apply to production of useful chemical substances. As described above, various chemical substances are able to be produced from plant material according to the present invention; this realization of biorefinery will be great contribution of the present invention.
  • low molecule saccharides are obtained from solid-state polysaccharides by conducting saccharification treatment.
  • the enzymatic saccharification treatment using cellulase is able to conduct the saccharification treatment sufficiently at small amount of enzyme.
  • the chemical substances from biomass source will be expected to have increasing popularity because it relates to drastically cost down of manufacture.
  • FIG. 1 is an approximate cross section depicting the microwave radiating device 10 of the present invention.
  • Microwave irradiating means consists of a microwave radiating source 11 and a waveguide 12; the waveguide 12 connects to a container 14 with a removable means.
  • the container 14 has a microwave receiving section 16 at above space of paper as showed in FIG. 1 .
  • the microwave receiving section 16 is shielded by dielectric material 18.
  • the dielectric material 18 is sandwiched by two pieces of sheet shaped parts 20.
  • the container 14 has a supply entrance 22 as a supply means and a discharge exit 24 as discharge means.
  • the said microwave represents short wavelength portion among electromagnetic wave; to be concretely saying, the wavelength is at frequency of 300 MHz - 30 GHz.
  • the said microwave is not only the frequency described above but also other frequency in addition to that said frequency.
  • the said microwave radiating source 11 represents a substance which generates microwave; to be concretely saying, klystron or magnetron, IMPATT diode, gun diode etc. may be used.
  • the microwave radiating source 11 connects to microwave receiving section 16 of the container 14 through a waveguide 12 as showed in FIG. 1 , but it may connect directly to microwave receiving section 16 of the container 14 without a waveguide 12.
  • the said waveguide 12 is a tube for making microwave generated at microwave radiating source go through inside. To prevent microwave from escaping to outside, it is desirable that the waveguide 12 is made of non-dielectric material which can not be penetrated by microwave.
  • the materials which can be used to form the waveguide 12 are stainless, aluminium, titanium, nickel, gold, silver etc..
  • the microwave radiating means which has microwave radiating source 11 and the waveguide 12 to be main components, may connect with container 14 in removable mode.
  • the connecting manner may use pressure clamp etc..
  • the container 14 has a microwave receiving section 16 at wave guide direction (above space of paper of FIG. 1 ).
  • the microwave receiving section makes microwave penetrate into the container 14 through a dielectric material 18 as a medium.
  • the microwave receiving section 16 may be for example, a structure that shields the opening installed at microwave waveguide direction of the container 14 with dielectric material 18.
  • the said dielectric material 18 is a material which has a property that microwave can be penetrated easily, to be concretely saying, may use quartz glass, fluorocarbon polymers, ceramics, alumina, sapphire, and diamond etc.. Thus microwave passes through the waveguide 12 will enter into the container 14 from the microwave receiving section 16 because it can penetrate the dielectric material 18.
  • the properties or shapes of the dielectric material 18 may be chosen by the users freely to meet the purpose of using microwave radiating device. Because the waveguide 12 and the container 14 are connected in removable mode, it is easy to exchange the dielectric material 18 with the most suitable substance.
  • the dielectric material 18 is sandwiched by sheet shaped parts.
  • the sheet shaped parts may be composed of either dielectric material or non-dielectric material.
  • the dielectric material may use quartz glass, fluorocarbon polymers, ceramics, alumina, sapphire, and diamond etc.
  • the sheet shaped parts 20 of non-dielectric material must have a structure such as a hole that is able to let microwave penetrate. Because it is necessary to protect the dielectric material 18, it will be desirable that substances of composing the sheet shaped parts 20 possess better strength than that of the dielectric material 18.
  • the dielectric material 18 is laminated either at one side of the sheet shaped parts 20 or at both sides to make a sandwich.
  • the dielectric material 18 is protected by being sandwiched, manufacture or maintenance of the microwave radiating device become easy. Further, the properties or shapes of the sheet shaped parts 20 may be chosen by the users freely to meet the purpose of using microwave radiating device. Because the waveguide 12 and the container 14 are connected in removable mode, it is east to exchange the sheet shaped parts 20 with the most suitable substance.
  • the container 14 has a structure to prevent microwave from escaping by installing at least one layer composed of non-dielectric material between atmosphere of the inner side and the outer side of the container.
  • the said non-dielectric material represents a material which has a property that microwave can not penetrate. Concretely materials such as stainless, aluminium, titanium, nickel, gold, silver etc. can be used.
  • Outer shell of the container 14 may be made of either at least one layer of the non-dielectric material or multilayer structure that has other layer at inner side or outer side atmosphere of the layer of the non-dielectric material. Further, surface of the outer shell of the container 14 which is composed of dielectric material may be coated with a layer of non-dielectric material.
  • Microwave penetrates the microwave receiving section 16 of the dielectric material 18 and enters the container 14, at the time when microwave contacts radiated material it is absorbed by the radiated material. Further, microwave that is not absorbed by the radiated material is reflected at inner wall of the container 14 and moved inside of the container 14. Because the container 14 has installed a layer composed of non-dielectric material as described above microwave can not escape to outside of the container and decrease energy loss.
  • the container 14 has a supply entrance 22 as a supply means and a discharge exit 24 as discharge means.
  • the radiated material is given into the container 14 from the supply entrance 22 by a pump pressure, and discharged to outside of the container 14 from the discharge exit 24 after the irradiation of microwave.
  • the numbers of the supply entrance 22 and the discharge exit 24 has no limit and can be prepared to meet the objects of usage.
  • the number of the supply entrance 22 may be the same as the number of the kinds of the radiated materials, and the ratio of mixed amount of the radiated materials can be managed by supplying amount.
  • the discharge exit 24 also has plural number to respond to treatment after irradiation.
  • the connecting type microwave radiating device according to the present invention is a combination device that combines microwave radiating device 10 mentioned above with removable means.
  • the removable means may use pressure clamp etc.. Further, the number of connecting microwave radiating device can be established freely to meet user's demands of microwave treatment amount.
  • the dielectric material 18 which shields the microwave radiating source 11 or microwave receiving section is optimized for preventing microwave from counteracting each other.
  • the microwave radiating device and the connecting type microwave radiating device according to the present invention have various usages, for example, enhancement and high yield rate of chemical reaction, pretreatment of biomass raw material such as grain residue or disused wood etc., sterilization of food or medicine, extraction or dehydration of a substance etc..
  • FIG. 2 is depicting the connecting type microwave radiating device 100 of the present invention and related peripheral equipments.
  • This connecting type microwave radiating device 100 is a combination device wherein three microwave radiating devices of the present invention, e.g. 10a, 10b, and 10c, are connected.
  • FIG. 3 is a partial cross section (looking direction is perpendicular to the paper) depicting the above connecting type microwave radiating device 100.
  • FIG. 4 is a partial cross section (looking direction is perpendicular to the paper) depicting a microwave radiating device which is installed at the center of the above connecting type microwave radiating device 100.
  • the microwave radiating source 11 connects to one end 12a of the waveguide 12.
  • the other end 12b of the waveguide 12 connects to container 14b.
  • a power monitor 118 is installed in the waveguide 12 to measure the electricity of microwave that enters into the waveguide 12.
  • the waveguide 12 has an edge 302 at container brim 12b.
  • the edge 302 is protruding towards diameter direction, and forms a unity as a portion of the waveguide 12.
  • the container 14b also has an edge 306 at upper side of the microwave receiving section 16.
  • the edge 306 is also protruding towards diameter direction.
  • the edge 302 of the waveguide 12 has a conjugating section 303, and the edge 306 of the container 14b also has a conjugating section 307, and both edges are able to conjugate to each other.
  • a gap 309 is provided at conjugating section 307 of the edge 306 of the container 14b, annular elastic parts 308 such as O-ring is inserted into the gap 309.
  • annular elastic parts 308 such as O-ring is inserted into the gap 309.
  • the microwave receiving section 16 of the container 14b is shielded by glass 18 which is a dielectric material.
  • the container 14b has a glasshousing section 313, and the glass 18 is kept in the glasshousing section 313. Furthermore, glass 18 is sandwiched by gasket 20a, and 20b which are sheet shaped parts composed of polytetrafluoroethylene.
  • gasket 20a, and 20b which are sheet shaped parts composed of polytetrafluoroethylene.
  • the microwave receiving section 16 has a protruding section 315
  • the diameter of the microwave receiving section 16 is smaller than that of the glass 18 and the gasket 20a, and 20b. Therefore the protruding section 315 bears the glass 18 and the gasket 20a, and 20b. The result is that the glass 18 and the gasket 20a, and 20b would not fall into the container 14b.
  • the pressure that makes the waveguide 12 and the container 14b fix is transmitting to upper gasket 20a, glass 18, and lower gasket 20b through the spacer 316.
  • the lower gasket 20b contacts to protruding section 315 counterforce to above pressure is transmitting to lower gasket 20b, glass 18, and upper gasket 20a.
  • glass 18, and gasket 20a, 20b are also fixed in up and down directions without using special conjugating means.
  • microwave treatment should be able to endure the pressure from the container 14b or waveguide 12, to be implemented even under the severe condition such as high pressure or decompression, vacuum etc..
  • the gasket 20a, 20b have better strength than that of the glass 18, the glass 18 is protected by the gasket 20a, 20b.
  • the container 14b provides one supply entrance 22b and one discharge exit 24b respectively.
  • the supply entrance 22b has an edge 321.
  • the shape of the edge 321 is protruding to diameter direction.
  • the discharge exit 24a of the microwave radiating device 10a at left side also has an edge 325.
  • the shape of the edge 325 is protruding to diameter direction too.
  • the edge 321 at the supply entrance 22b side has a conjugating section 320
  • the edge 325 at the discharge exit 24a has a conjugating section 323, and both edges are conjugating sections and are able to conjugate to each other.
  • a gap 327 is provided at conjugating section 323 of the edge 325 of the discharge exit 24a, an annular elastic parts 326 such as O-ring is inserted into the gap 326.
  • an annular elastic parts 326 such as O-ring is inserted into the gap 326.
  • the discharge exit 24b connects to the supply entrance 22c of the microwave radiating device10c showing at right side of the paper of FIG. 4 .
  • the discharge exit 24b is equivalent to the discharge exit 24a of the microwave radiating device 10a
  • the supply entrance 22c is equivalent to the supply entrance 22b of the microwave radiating device 10b. Therefore the discharge exit 24b and the supply entrance 22c may connect in removable mode by the same connecting manner as the discharge exit 24a and the supply entrance 22b mentioned above.
  • the radiated material is thrown into a raw material tank 102, and mixed uniformly by a raw material mixer 104, then delivered to a supply pump 106.
  • the supply pump 106 pressurizes to push the radiated material out. Then the radiated material delivered to the pump 106 goes through a supply tube 108, and reaches the internal space of a reacting tube 202.
  • the reacting tube 202 is composed of an anterior reacting chamber 204, and three containers of the microwave radiating device 14a, 14b, 14c, and a posterior reacting chamber 205.
  • the radiated material that has gone through the supply tube 108 reaches the anterior reacting chamber 204.
  • a reacting stirring stick 210 is installed along the axis direction of the interior of the reacting tube 202.
  • Multiple impellers are mounted on this reacting tube 202 along the axis of the tube. These impellers will display screw effect during the time that the reacting stirring stick 210 rotates.
  • the reacting stirring stick 210 is rotated by a motor of a reacting mixer 110, the radiated material is mixed uniformly meanwhile delivered from left side to right side of the paper of FIG. 3 .
  • Microwave irradiates from microwave radiating means of three microwave radiating devices 10a, 10b, 10c.
  • thermometers In the container 14a, 14b, and 14c, there are provided thermometers to manage the temperature of the interior of the reacting tube 202 one by one.
  • the radiated material that had been irradiated by microwave is delivered to posterior reacting chamber 205.
  • the radiated material that is delivered to the posterior reacting chamber 205 is discharged to outside of the device from a control valve 204.
  • a pressure adjuster 214 At the control valve 204 there is joined a pressure adjuster 214 to adjust the internal air pressure of the reacting tube 202.
  • the control of the connecting type microwave radiating device is undertaken by a system control panel 120 and a microwave control panel 122.
  • the system control panel 120 executes control of the raw material agitator 104, the supply pump 106, the reacting mixer 110, and the pressure adjuster 214.
  • the internal temperature of the reacting tube is measured by the thermometer, and transmitted to the system control panel 120.
  • the microwave control panel 122 executes control of the microwave radiating source 11.
  • the measured result of power-monitor 118 is transmitted to the microwave control panel 122.
  • the system control panel 120 and the microwave control panel 122 exchange data information to each other, and compel the connecting type microwave radiating device to work appropriately.
  • the connecting type microwave radiating device can be either that is composed of more than three of microwave radiating devices, or that microwave radiating source and container directly join without using waveguide in each microwave radiating device.
  • the method comprises a separation process which obtains a mixture through microwave radiating on plant material which at least contains lignocellulose at existence of Lewis acid catalyst, the mixture contains decomposed products of lignin and glycocomponent that at least contains solid state polysaccharides; and a separation process which obtains a mixture through microwave radiating on plant material which at least contains lignocellulose at existence of molybdic acid ion, ammonium ion and peroxides, the mixture contains decomposed products of lignin and glycocomponent that at least contains solid state polysaccharides.
  • the said lignocellulose represents botanical organic compounds which is composed of polysaccharides such as cellulose, hemicellulose etc.. Because the polysaccharides such as cellulose, hemicellulose etc. are used as resource, to separate saccharides and lignin, namely to destroy the insulation of lignin over polysaccharides, is effective. Particularly if there is attempt to make lignocellulose convert to useful substances such as ethanol etc. by enzymatic saccharification treatment and fermentation, the pretreatment that destroy the insulation of lignin over polysaccharides is necessary.
  • Non-Pattern document 2 the method of conducting pretreatment by means of microwave irradiating in water solution of acetic acid
  • Patent document 5 the method of conducting separation, decomposition of lignin by implement microwave irradiating at existence of oxidant
  • attern document 6 the method of accelerating the speed of de-lignin during digestion
  • Non-Pattern document 3 the method of combining microwave treatment and alkaline treatment
  • the lignin of conifer is hard to decompose.
  • decomposition of the lignin of conifer is not sufficient, the amount of obtained glycocomponent is very small (non-Pattern document 4).
  • the treatment temperature is over 200°C by the traditional method, the problems are huge energy consumption and large amount of over-decomposed products of saccharides (non-Pattern document 4).
  • the objects of the present invention are to provide a method of producing glycocomponent from plant material: the method being able to produce glycocomponent efficiently meanwhile preventing over-decomposition of saccharides in condition of low environment impact; to obtain polysaccharides by sufficient saccharification under condition of using small amount of enzyme.
  • the objects of the present invention are to provide a method of producing glycocomponent from plant material: the method being able to produce glycocomponent efficiently meanwhile preventing over-decomposition of saccharides in condition of low environment impact; to obtain polysaccharides by sufficient saccharification under condition of using water as dispersing medium or using small amount of enzyme.
  • the present invention is related to a method of producing glycocomponent from plant material: the method comprises a separation process which obtains a mixture through microwave radiating on plant material at existence of Lewis acid catalyst; the plant material at least contains lignocelluloses; the mixture contains decomposed products of lignin and glycocomponent that at least contains solid state polysaccharides. Further, the present invention is related to a method of producing glycocomponent from plant material: the method comprises a separation process which obtains a mixture through microwave radiating on plant material at existence of molybdic acid ion, ammonium ion and peroxides; the plant material at least contains lignocelluloses; the mixture contains decomposed products of lignin and glycocomponent that at least contains solid state polysaccharides.
  • the method of producing glycocomponent from plant material according to the present invention is characterized by molecule diminishment of lignon in lignocellulose, decoupling of the linkage between lignin and polysaccharides, change of the structure of polysaccharide crystal, leaching of hemicellulose etc..
  • the glycocomponent and the lignin are separated through molecule diminishment of lignon in lignocellulose, decoupling of the linkage between lignin and polysaccharides, change of the structure of polysaccharide crystal, leaching of hemicellulose etc.. Therefore the mixture obtained by this process comprises glycocomponent which contains monosaccharide or solid state polysaccharides such as cellulose etc., and decomposition products of lignin in dissolution condition.
  • the method of producing glycocomponent from plant material according to the present invention further comprises extraction process to extract the above solid state polysaccharides obtained by using biomass from the above mixture.
  • a mixture, that contains decomposed products of lignin and glycocomponent which at least has solid state polysaccharides, is obtained; by means of irradiating microwave at the existence of Lewis acid to plant material that has at least lignocellulose.
  • the method of producing glycocomponent from plant material according to the present invention a mixture, that contains decomposed products of lignin and glycocomponent which at least has solid state polysaccharides, is obtained; by means of at the existence of molybdic acid ion, ammonium ion and peroxides irradiating microwave to plant material which has at least lignocellulose.
  • the mixture obtained from the process comprises decomposed products of lignin and glycocomponent which has at least solid state polysaccharides.
  • the decomposed products of lignin comprises aromatic compounds such as phenol etc..
  • the glycocomponent which has at least solid state polysaccharides consists of low molecule saccharides such as monosaccharides or oligosaccharides etc. in addition to solid state polysaccharides such as cellulose, hemicellulose etc..
  • the solid state polysaccharides contained in the glycocomponent are converted to low molecule saccharides by conducting saccharification treatment. Further, it is able to produce useful chemical substances such as ethanol, methane, succinic acid, itaconic acid, lactic acid etc. by conducting fermentation treatment etc.. Further, it is also possible to produce useful chemical substances from the low molecule saccharides contained in glycocomponent or the decomposed products of lignin.
  • the irradiation of microwave in this process is a mode of heating wherein radiation causes oscillation effect of electromagnetic field on charged particle or electric dipole inside of substance of plant material; makes particle rotate or oscillate, then self-heat from interior.
  • This mode the heating is different from that of external heating source, it is able to heat the plant material rapidly and uniformly, almost ignores the effects of thermal conduction or convection.
  • microwave represents short wave length portion of the electromagnetic wave, comprising electromagnetic wave with wave length less than 1 m or submillimetric wave with wave length less than 1 mm which is close to far infrared.
  • the ideal frequency of microwave of the present invention is 300 MHz - 30 GHz, more ideal frequency of microwave is 2000 MHz - 6000 MHZ.
  • Microwave with frequency 2450 MHz or microwave with frequency 5800 MHz are used often.
  • microwave used in this process is not limited in the range of these frequencies, microwave beyond the range of these frequencies is used also.
  • the radiated material oscillates responding to the microwave, then the material generates heat itself because of frictional heat occurring by oscillation.
  • the effect of the present invention can be obtained in the range mentioned above, the most favorable mode is to optimize wave length and frequency of microwave in respond to the growing area, structure, and kinds etc. of the plant material as well as the method of pretreatment.
  • the plant material used as raw material in this process represents a material of botanical source comprising at least lignocellulose, further compring lignin, cellulose, hemicellulose.
  • the plant material is for example material of wood source or herb source etc..
  • the plant material of wood source may use a gymnosperm comprising conifer such as *cryptomeria, pine, Japanese cypress, buddhist pine, Cephalotaxus, Californian redwood, hiba arborvitae, Japanese yew etc., or ginkgo; an angiosperm comprising broad leaf trees such as beech tree, Japanese zelkova keyaki tree, camellia, Japanese oak, cherry tree, camphor tree, Castanopsis, maple tree, chestnut tree, eucalyptus, a locust tree etc..
  • the lignin that contained in the plant material of conifer source is mainly constituted by guaiacyllignin
  • the lignin that contained in the plant material of broad leaf tree source is mainly constituted by guaiacyllignin and syringyllignin.
  • the plant material of herb source may use bagasse which is residue of Saccharum officinarum, rice straw, wheat straw, rice husks etc..
  • the plant material used as raw material in this process may be managed by the methods well-known in the art and used in form of powder or chip, flake, fiber, lumber etc.. From the point of view about reaction efficiency the favorable plant material is manufactured to powder, chip, flake, or fiber.
  • the diameter of the particles during processing a plant material to particle is not limited, but favorable diameter would be 0.1 ⁇ m - 5 mm. Further, the size or thickness is not limited during processing a plant material to chip, but favorable size is 5 mm - 50 mm, and favorable thickness is 0.1 mm - 5 mm.
  • pretreatment which removes hydrophobic low molecules through refluxing mixed solution of alcohol and benzene; or removes hydrophilic low molecules through mixing with water and heating.
  • the above pretreatment may be omitted if high yield is secured at saccharification treatment.
  • the plant material may be used in this process either being dehydrated or being not dehydrated.
  • the Lewis acid catalyst used in this process represents a catalyst which has activity to receive electron-pair from reaction partner, excludes usual acid catalyst (inorganic acid such as hydrochloric acid, sulfuric acid etc. or organic acid such as phosphoric acid).
  • the Lewis acid may use metallic salt, halogen ides of metal, or oxides of metal, carboxylates etc..
  • aluminium compounds such as aluminium floride, aluminium chloride, aluminium bromide, aluminium iodide, aluminium sulfate etc.
  • copper compounds such as copper(I) fluoride, copper(II) fluoride, copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, copper(II) iodide, copper(I) sulfate, copper(II) sulfate etc.
  • iron compounds such as ferrous(Iron(II)) fluoride, ferric (Iron(III)) fluoride, ferrous chloride, ferric chloride, ferrous bromide, ferric bromide, ferrous iodide, ferric iodide, ferrous sulfate, ferric sulfate etc.
  • zinc compounds such as zinc floride, zinc chloride, zinc bromide, zinc iodide, zinc
  • At least one selected from the groups consists of aluminium chloride, aluminium bromide, aluminium sulfate, ferric chloride, zinc bromide, and zinc sulfate.
  • the compound which may be used as dispersing medium in this process is, for example, water or organic compounds.
  • compounds used as examples of the organic compounds such as glycerin, ethylene glycol, propylene glycol, methanol, ethanol, propanol, butanol, octanol, butandiol, trimethylolpropane, methylethyl ketone, acetylacetone, dimethyl sulfoxide, nitrobenzene etc. are given.
  • water or organic compounds singly, or using a mixture of water and organic compounds will be proper.
  • In the condition of using a mixture of water and organic compound it is favorable that 1 volume of water is mixed with 0.1 volume - 10 volume of the organic compounds. Further, it is also favorable that the dispersing medium contains acid or alkali.
  • microwave When microwave irradiates to the plant material at the existence of Lewis acid, for example, microwave may irradiate to the above plant material through the way that microwave irradiates to plant material in a dispersing liquid in which powder, chip of plant material are dispersed in above dispersing medium. But sometimes partial portion of plant material may dissolve in dispersing medium. It is acceptable that either Lewis acid catalyst is previously dissolved in dispersing medium before plant material is dispersed, or is added into dispersing medium after plant material has been dispersed.
  • the ratio by weight of the amount of plant material and the amount of dispersing medium in above dispersing medium is not limited.
  • the ideal ratio by weight may be that plant material vs. dispersing medium is 1:1 - 1:100, more ideal ratio by weight may be that plant material vs. dispersing medium is 1:5 - 1:20. If the amount of dispersing medium is small, the heating rate may slow down; on the other hand, if the amount of solvent is large, the amount of plant material for treatment becomes small, the producing cost becomes expensive.
  • the optimized amount of Lewis acid catalyst is varied according to the variety of plant material. For example, if the source of plant material is a beech tree, corresponding to 1 g of plant material, the ideal amount of Lewis acid catalyst is 1 ⁇ mol - 1000 ⁇ mol, more ideal amount is 60 ⁇ mol - 720 ⁇ mol, yet more ideal amount is 180 ⁇ mol - 360 ⁇ mol. If the amount of Lewis acid corresponding to plant material is insufficient, satisfied effect of separating saccharides and lignin may not be obtained; on the other hand, if the amount of Lewis acid corresponding to plant material is too much, the treatment of solvent becomes difficult after reaction.
  • the dispersing liquid is stirred by using a stirrer to secure that microwave radiates uniformly to the plant material which is dispersed in above dispersing medium.
  • the reaction time of implementing microwave radiation of this process has no limitation, but 1 minute to 60 minutes will be favorable. If the reaction time is short, the separation of saccharides and lignin will not be sufficient; on the other hand, if the reaction time is long, not only the cost is high but also the useful chemical substances are possibly decomposed.
  • the reaction temperature of implementing separation of saccharides and lignin of this process has no limitation, but to heat plant material at 80°C - 240°C will be favorable, and to heat plant material at 150°C - 180°C will be more favorable. If the reaction temperature is low, the separation of saccharides and lignin would not be sufficient; on the other hand, if the reaction temperature is high, the useful chemical substances are possibly decomposed. In accordance with the present invention, at a temperature that saccharides will not over-decompose, it is able to separate saccharides and lignin efficiently. Further, in the reaction of the present invention it is favorable to achieve a prescribed reaction temperature within short time by rapidly heating. If heating is rapid, by-products produced at low temperature are rare.
  • the ideal molybdic acid ion used in this process is an ion constituted by molybdenum atom and oxygen atom, to be concretely saying, compounds expressed with chemical formula MoO 4 2- , Mo 2 O 4 2- , Mo 6 O 19 2- , Mo 7 O 24 6- , are given as examples. Further, the ammonium ion used in this process is expressed with chemical formula NH 4 + .
  • microwave irradiates at existence of above molybdic acid ion, above ammonium ion, and peroxides.
  • the above two ions is obtained by dissolving molybdate salt and ammonium salt in a dispersing medium which is described later. It is favorable that in condition of dissolving ammonium molybdate the above two ions are able to obtain simultaneously. It is acceptable that either those salts are previously dissolved in dispersing medium before plant material is dispersed, or are added into dispersing medium and dissolve after plant material has been dispersed.
  • the peroxides may use hydrogen peroxide or metal salt of hydrogen peroxide, organic compounds having peroxy group etc.
  • Metal salt of hydrogen peroxide such as lithium peroxide, potassium peroxide, sodium peroxide, magnesium peroxide, calcium peroxide, barium peroxide etc. are given as examples.
  • hydrogen peroxides from the point of view of decrease cost, it is favorable to use hydrogen peroxide. It is acceptable that either those peroxides are previously dissolved in dispersing medium before plant material is dispersed, or are added into dispersing medium and dissolve or mix after plant material has been dispersed. Further, it is also favorable to generate peroxide in dispersing medium by using well-known method in the art such as anthraquinone method.
  • the dispersing medium which may be used in this process may be water, organic compounds, or their combination.
  • the organic compounds such as glycerin, ethylene glycol, propylene glycol, methanol, ethanol, propanol, butanol, octanol, butandiol, trimethyloloropane, methylethyl ketone, acetyl acetone, dimethylsulfoxide, nitrobenzene etc. are given as examples.
  • these compounds from the point of view of decreasing trouble of post-treatment and the cost, it is favorable to use water as dispersing medium. Further, it is also favorable that dispersing medium contains acid or alkali.
  • microwave When microwave irradiates to the plant material at the existence of molybdic acid ion, ammonium ion, and peroxides, for example, microwave may irradiate to the above plant material through the way that microwave irradiates to plant material in a dispersing liquid wherein powder, chip of plant material are dispersed in above dispersing medium. But sometimes partial portion of plant material may dissolve in dispersing medium.
  • the optimized concentration of molybdic acid ion, ammonium ion, and peroxide is varied according to the variety of plant material.
  • the ideal final concentration of molybdic acid ion and ammonium ion vs. plant material such as beech tree is 0.01 mM - 100 mM; more ideal concentration is 0.1 mM - 10 mM; yet more ideal concentration is 0.25 mM - 5 mM.
  • the deal final concentration of peroxide vs. plant material such as beech tree is 0.01 M - 10 M; more ideal concentration is 0.1 M - 1 M. If their concentration is low, the separation of saccharides and lignin will not be sufficient; on the other hand, if their concentration is high, the treatment of solvent becomes difficult after reaction.
  • the ratio by weight of the amount of plant material and the amount of dispersing medium in above dispersing medium is not limited.
  • the ideal ratio by weight may be that plant material vs. dispersing medium is 1:1 - 1:100, more ideal ratio by weight may be that plant material vs. dispersing medium is 1:5 - 1:20. If the amount of dispersing medium is small, the heating rate may slow down; on the other hand, if the amount of solvent is large, the amount of plant material for treatment may be small, the producing cost becomes expensive.
  • the dispersing liquid is stirred by using a stirrer to secure that microwave radiates uniformly to the plant material which is dispersed in above dispersing medium.
  • the reaction time of implementing microwave radiation of this process has no limitation, but 1 minute to 60 minutes will be favorable. If the reaction time is short, the separation of saccharides and lignin will not be sufficient; on the other hand, if the reaction time is long, not only the cost is high but also the useful chemical substances are possibly decomposed.
  • the reaction temperature of implementing separation of saccharides and lignin of this process has no limitation, but to heat plant material at 50°C - 240°C will be favorable, and to heat plant material at 80°C - 180°C will be more favorable. If the reaction temperature is low, the separation of saccharides and lignin would not be sufficient; on the other hand, if the reaction temperature is high, the useful chemical substances are possibly decomposed. In accordance with the present invention, at a temperature that saccharides will not over-decompose, it is able to separate saccharides and lignin efficiently. Further, in the reaction of the present invention it is favorable to achieve a prescribed reaction temperature within short time by rapidly heating. If heating is rapid, by-products produced at low temperature are rare.
  • the present invention comprises an extraction process in which solid state polysaccharides are extracted from the mixture obtained in separation process (1).
  • the mixture obtained in separation process (1) at least comprises decomposed products of lignin that dissolved in dispersing medium, and solid state polysaccharides that is composed of cellulose, hemicellulose etc..
  • this process it is able to extract insoluble component of solid state polysaccharides that is composed of cellulose, hemicellulose etc..
  • the insoluble component except solid state polysaccharides there may remain lignin which is not decomposed in above separation process.
  • decomposed products of lignin contained in above mixture or low molecule saccharides obtained from glycocomponent are also used to produce useful chemical substances.
  • the solid state polysaccharides are able to extracted by using technique of filtration etc. in this process.
  • the mixture obtained in separation process (1) is directed through a porous filter medium; and the solid state polysaccharides which can not pass porosity are extracted from dispersing medium.
  • the filter medium may use filter paper, glass fiber filter, membrane filter, filtration plate etc..
  • the favorable filter medium that can be used in this process is favorable to select suitable diameter of porosity to catch obtained solid state polysaccharides reliably.
  • filter medium that holds particles of 1 ⁇ m - 50 ⁇ m is used.
  • pressure filtration such as decompression, pressurization, centrifugation etc.
  • the solid state polysaccharides extracted in this process are able to convert to low molecule saccharides through saccharification treatment in which an enzyme such as cellulase may be used.
  • an enzyme such as cellulase may be used.
  • microbes to perform fermentation treatment it is able to obtain useful compounds such as ethanol, methane, succinic acid, itaconic acid, lactic acid etc. from the obtained low molecule saccharides.
  • useful chemical substances such as aromatic compounds from decomposed products of lignin which is contained in the residue mixture after extraction of solid state polysaccharides.
  • the solid state polysaccharides are extracted, besides in the condition that the solid state polysaccharides and the decomposed products of lignin are mixing together the saccharification treatment of the solid state polysaccharides may still be conducted.
  • the saccharizied mixture obtained from saccharification treatment may have decomposed products of lignin and low molecule saccharides.
  • the mixture may be used as raw material either in the condition of mixture, or after separating the decomposed products of lignin and the low molecule saccharides respectively by chromatography or other methods.
  • the treatment of radiated material is conducted by using a connecting type microwave radiating device in which three microwave radiating devices are connected as showing in FIG. 2 .
  • the frequency of microwave is 2450 MHz; output of the microwave radiating device 10a is 1.2 kW; output of the microwave radiating device 10b is 0.9 kW; output of the microwave radiating device 10c is 0.8 kW.
  • the radiated material is powder of cryptomeria which has past through a sieve of 48 mesh.
  • the solvent is a mixture of ethylene glycol and phosphoric acid at a ration 95:5 by volume.
  • the powder of cryptomeria and the solvent which is 11 times of weight of the powder of cryptomeria are mixed uniformly in the raw material tank 102.
  • the radiated material is sent into the supply pump 106, then goes through the supply tube 108 by pressurizing the supply pump 106, and achieves the interior of the reacting tube 202.
  • the pressure of the interior of the reacting tube 202 is 1.5 MPa due to pressurizing the supply pump 106.
  • the radiated material which is sent to anterior reacting chamber 204 is transported into the reacting tube 202 meanwhile receiving microwave irradiation treatment. Once the radiated material is sent into the supply pump 106, until it is discharged out from control valve 204, the time spent is 23 minutes. The temperature change of the radiated material during this period of time is shown in FIG. 6 . Further, the treatment amount of the radiated material including the weight of solvent is 13.4 kg/hour.
  • the treated substance which is discharged outside of the device is centrifuged to separate solvent, then washed with acetone and water, then conducted quantitative analysis of the amount of holocellulose in the treated substance. Then the saccharification treatment of the treated substance is conducted. The treated substance is picked 0.5 g of dried weight to conduct quantitative analysis of holocellulose by sodium chlorite method. Then saccharification treatment of the treated substance is conducted. In a centrifuge tube, gather dry weight 0.2 g of treated substance. Add 8 FPU of "Meicelase” (registered trademark, Meiji Seika Company) that is cellulase, and 1 M of acetic acid buffer solution (pH 4.5), make final concentration be 50 mM and total amount be 10 mL (solid portion 2%).
  • 1 L of batch type microwave radiating device is used in the microwave treatment of comparison.
  • the treatment of radiated material is performed by the same method as the embodiment 1, and radiated material including solvent in total weight of 1080 g is treated.
  • the radiated material is heated to 190°C within 12 minutes, and kept at 190°C for 15 minutes.
  • the temperature change of the radiated material of the comparison 1 is shown in FIG. 6 .
  • the frequency of radiating microwave is 2450 MHz; output is 1.5 kW; the pressure inside the reaction container is 0.2 MPa.
  • microwave treatment at high temperature high pressure may be performed and high saccharification rate of the treated substance may be obtained by using the microwave radiating device and the connecting type microwave radiating device according to the present invention. Further, as shown in FIG. 6 compare to the microwave radiating device used in comparison, in the microwave radiating device of the present invention the radiated material may be heated in shorter time.
  • the lumber of beech tree which is raw material of the plant material is crushed in a wood shredder and a Wiley mill, divided with a sieve; powder (beech tree powder) of size 355 ⁇ m to 500 ⁇ m is collected.
  • the beech tree powder is mixed with a mixture of ethanol/benzene (1/2 by volume) which is 2 times by volume of the volume of the beech tree powder, then refluxed.
  • the hydrophobic low molecule substances are removed by refluxing.
  • the beech tree powder is mixed with water which is 2 times by volume of the volume of the beech tree powder, and treated at 121°C, about 30 minutes in an autoclave.
  • the hydrophilic low molecule substances are removed.
  • the prepared beech tree powder is used as plant material, and is used in embodiments and comparisons in the following.
  • Embodiment 1 - 7 Put 1 g of the prepared beech tree powder, and 20 g of 1-propanol/water (1/1 by volume) to be dispersing medium into a vial for microwave radiating; in Embodiment 1 - 7, add separately 60 ⁇ mol of various Lewis acid catalyst as listed in Table 1; obtain dispersing liquids. The comparison 1 has no catalyst added.
  • the above vials are tightly sealing; while stirring with a stirrer at 900rpm, use microwave radiating device "Initiator 60" (manufactured by Biotage Japan Company) which irradiates microwave of 2450 MHz at condition of 30 minutes, 180°C to the above each dispersing liquid.
  • the liquid is filtered by using filter paper "Advantec No. 131" (registered trademark, manufactured by Toyo Filter Paper Company, holding particle diameter 3 ⁇ m); an insoluble component which contains solid state polysaccharides and remaining lignin is obtained.
  • the wet weight of the insoluble component is measured, then the water is removed completely by drying the component, find out the hydration rate.
  • the weight of the insoluble component is calculated by deducting the weight of water from the wet weight; the ratio (the yield of the insoluble component) of the weight of the insoluble component and the weight of the used wood powder is calculated.
  • the embodiments 1 - 7 have lower yield of insoluble component, but have higher saccharide yield corresponding to the unit weight of insoluble component and higher the saccharide yield corresponding to the unit weight of the plant material.
  • a microwave radiating vial put 1g of the prepared beech tree powder and 20 g of 1-propanol/water (1/1 by volume) to be dispersing medium; add 60 ⁇ mol of aluminum sulfate as Lewis acid; obtain a dispersing liquid.
  • the above vial is tightly sealing; and while stirring with a stirrer at 900rpm, use a microwave radiating device "Initiator 60" (Biotage Japan) which irradiates microwave of 2450 MHz at two conditions of 30 minutes, 160°C and 30 minutes, 180°C to irradiate the above dispersing liquid (embodiment 8).
  • the above dispersing liquid is put in an autoclave cylinder. External heating is conducted in autoclave at two conditions of 30 minutes, 160°C and 30 minutes, 180°C (comparison 2).
  • the enzymatic saccharification treatment is performed by using 1 FPU and 8 FPU of "Meicelase” (registered trademark) to conduct enzymatic saccharification of the embodiment 8 and the comparison 2 respectively.
  • the FIG. 7 indicates the saccharide yield corresponding to the weight of plant material of the embodiment 8 and the comparison 2. No matter at what condition, the yield of the embodiment 8 being treated by microwave is higher. Especially the difference is obvious at the condition of small amount of enzyme. Therefore according to the present invention it is able to obtain saccharides with high yield even though the amount of enzyme used for saccharification of treated substance is small; thus drastically cut down of saccharification cost will be realized.
  • the gas chromatography mass spectrometry of soluble component id performed.
  • a microwave radiating vial put 1 g of the prepared beech tree powder to be plant material, and 20 g of 1-propanol/water (1/1 by volume) to be dispersing medium; add 60 ⁇ mol of aluminum chloride as Lewis acid catalyst; obtain a dispersing liquid.
  • the above vials are tightly sealing, stirring with a stirrer at 900 rpm, use a microwave radiating device "Initiator 60" (made by Biotage Japan Company) which irradiates microwave of 2450 MHz at condition of 30 minutes, 180°C to the above dispersing liquid (embodiment 9).
  • the above dispersing liquid is put in an autoclave cylinder. External heating is conducted in autoclave at condition of 30 minutes, 180°C (comparison 3).
  • reaction liquid which is filtered by using a filter paper "Advantec No. 131" (registered trademark, manufactured by Toyo Filter Paper Company, holding particle diameter 3 ⁇ m), is conducted gas chromatography mass spectrometry (GCMS).
  • GCMS gas chromatography mass spectrometry
  • the FIG. 8 indicates the result of GCMS.
  • Both of the embodiment 9 and the comparison 3 contain aromatic compounds of lignin source.
  • the embodiment 9, in addition to aromatic compounds, also contains much saccharide such as pentose or hexose, while the comparison 3 contains much decomposed product of saccharide such as 5-hydroxymethylfurfural (Retention time : 6.8 min - 7.0 min). Consequently, it is understood that saccharide is over-decomposed due to external heating in the comparison 3.
  • those saccharides may be utilized.
  • 5-hydroxymethylfurfural is inhibited by microwave treatment.
  • 5-hydroxymethylfurfural may obstruct ethanol fermentation of saccharides. Therefore the present invention is able to inhibit the formation of 5-hydroxymethylfurfural, and to conduct enzymatic saccharification or ethanol fermentation efficiently.
  • the lumber of cryptomeria which is raw material of the plant material is crushed in a wood shredder and a Wiley mill, and divided with a sieve; powder (cryptomeria powder) of size 500 ⁇ m to 1190 ⁇ m is collected.
  • the cryptomeria powder prepared above is used as plant material in the following embodiments and comparisons.
  • the plant material used in these embodiments are different from the embodiments 1 - 9; the hydrophobic low molecule and hydrophilic low molecule are not removed, production of saccharide is more difficult.
  • Embodiment 10-17 add ammonium chloride to be Lewis acid catalyst separately in various amount corresponding to 1 g of plant material as listed in Table 2; obtain dispersing liquids.
  • the comparison 4 has no catalyst added.
  • the above vials are tightly sealing; while stirring with a stirrer at 900 rpm, use a microwave radiating device "Initiator 60" (manufactured by Biotage Japan Company) which irradiates microwave of 2450 MHz at condition listed in Table 2.
  • the liquid is filtered by using filter paper "Advantec No. 131" (registered trademark, manufactured by Toyo Filter Paper Company, holding particle diameter 3 ⁇ m); an insoluble component is obtained.
  • the wet weight of the insoluble component is measured, then the water is removed completely by drying the component, find out the hydration rate.
  • the weight of the insoluble component is calculated by deducting the weight of water from the wet weight; the ratio (the yield of the insoluble component) of the weight of the insoluble component and the weight of used plant material is calculated.
  • the lumber of beech tree which is raw material of the plant material is crushed in a wood shredder and a Wiley mill, divided with a sieve; powder (beech tree powder) of size 355 ⁇ m to 500 ⁇ m is collected.
  • the prepared beech tree powder is plant material and is used in the following embodiments and comparisons.
  • the liquid is filtered by using filter paper "Advantec No. 131" (registered trademark, manufactured by Toyo Filter Paper Company, holding particle diameter 3 ⁇ m); an insoluble component which contains solid state polysaccharide and remaining lignin is obtained.
  • the wet weight of the insoluble component is measured, then the water is removed completely by drying the component, find out the hydration rate.
  • the weight of the insoluble component is calculated by deducting the weight of water from the wet weight; the ratio (the yield of the insoluble component) of the weight of the insoluble component and the weight of the used wood powder is calculated.
  • (A) ammonium molybdate has the highest saccharide yield compared with other ammonium salts.
  • Apropos of (B) ammonium phosphate dibasic or (C) ammonium hydrogen carbonate, (D) ammonium carbonate also has higher saccharide yield. From these results it is considered that through the separation process in which molybdic acid ion, ammonium ion and peroxides are used, solid state polysaccharide which can produce saccharide efficiently is obtained.
  • the above vials are tightly sealing; and while stirring with a stirrer at 900 rpm, use a microwave radiating device "Initiator 60" (Biotage Japan) which irradiates microwave of 2450 MHz at condition of 30 minutes, 140°C.
  • Enzymatic saccharification of using 2FPU, 4FPU, 6FPU, and 8FPU of "Meicelase” (registered trademark) is performed on the insoluble component which is obtained from the separation process wherein the same treatment as the embodiment 1 is conducted except microwave radiating is at 160°C, 9 minutes.
  • the saccharide yield corresponding to unit weight of insoluble component and the saccharide yield corresponding to unit weight of plant material are shown in FIG. 9 .
  • high saccharide yield is obtained even at 2 FPU - 4 FPU of enzyme. Therefore the solid state polysaccharide contained in insoluble component is obtained by the present invention, and is able to be saccharized even at small amount of enzyme, thus it may achieve huge cost-down of saccharification.
  • the saccharide yield of microwave radiating (embodiment 2) according to the present invention and external heating (comparison 2) are compared. Separation process of the embodiment 2 is performed as follow.
  • a microwave radiating vial put 1 g of the prepared beech tree powder and 20 g of water to be dispersing medium; add separately ammonium molybdate to make final concentration as entering in Table 3, and add hydrogen peroxide to make final concentration be 0.88 M; obtain dispersing liquid.
  • the above vials are tightly sealing; and while stirring with a stirrer at 900 rpm, use a microwave radiating device "Initiator 60" (Biotage Japan) which irradiates microwave of 2450 MHz at condition of 30 minutes, 140°C to the above dispersing liquid.
  • the separation process of the comparison 2 is performed as follow.
  • an autoclave cylinder put 1 g of the prepared beech tree powder and 20 g of water to be dispersing medium; add separately ammonium molybdate to make final concentration be as listed in Table 3, and add hydrogen peroxide to make final concentration be 0.88 M; obtain dispersing liquids.
  • the above cylinders are heated externally by using an autoclave at condition of 30 minutes, 140°C.
  • the lumber of cryptomeria which is raw material of the plant material is crushed in a wood shredder and a Wiley mill, and divided with a sieve; powder (cryptomeria powder) of size 500 ⁇ m to 1190 ⁇ m is collected.
  • the cryptomeria powder prepared like above is used as plant material in the following embodiment and comparison.
  • Separation process of the embodiment 3 is performed through irradiating microwave at the same condition as the embodiment 2, except using 1g of the prepared cryptomeria powder, adding ammonium molybdate which has various final concentrations as listed in Table 4. Further, separation process of the comparison 3 is performed through externally heating at the same condition as the comparison 2, except using 1g of the prepared cryptomeria powder, adding ammonium molybdate which has various final concentrations as listed in Table 4.
  • the dispersing liquids of (A) - (D) are obtained through adding ammonium molybdate to make final concentration be 1mM, and adding hydrogen peroxide individually of concentration as listed in Table 7.
  • the above vials are tightly sealing; and while stirring with a stirrer at 900 rpm, use a microwave radiating device "Initiator 60" (Biotage Japan) which irradiates microwave of 2450 MHz at condition of 30 minutes, 140°C to the above dispersing liquids.
  • the obtained insoluble component is extracted by extraction process, and is conducted to enzymatic saccharification treatment through using 8 FPU of "Meicelase” (registered trademark).
  • the dispersing liquids are obtained through adding ammonium molybdate to make final concentration be 1 mM, and adding hydrogen peroxide individually of concentration of 0.88 M.
  • the above vials are tightly sealing; and while stirring with a stirrer at 900 rpm, use a microwave radiating device "Initiator 60" (Biotage Japan) which irradiates microwave of 2450 MHz to the above dispersing liquids at reaction temperature of 140°C, reaction time as listed in Table 8.
  • the obtained insoluble component is extracted by extraction process, and is conducted to enzymatic saccharification treatment through using 8FPU of "Meicelase” (registered trademark).
  • the method of separating glycocomponent from plant material may make contribution to the realization of biofinery that obtains useful chemical substances such as ethanol or aromatic compounds etc. from biomass raw material.
  • the present invention may also apply to reducing plant material to pulp or bleaching of pulp.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Toxicology (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Saccharide Compounds (AREA)
  • Constitution Of High-Frequency Heating (AREA)
  • Processing Of Solid Wastes (AREA)
EP09802939.0A 2008-07-28 2009-07-28 Mikrowellenbestrahlungsgerät Active EP2323461B1 (de)

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JP2009013689 2009-01-23
JP2009072933 2009-03-24
PCT/JP2009/063398 WO2010013696A1 (ja) 2008-07-28 2009-07-28 マイクロ波照射装置、連結型マイクロ波照射装置、及び植物材料から糖成分を製造する方法

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EP2323461A4 EP2323461A4 (de) 2016-01-27
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012168681A1 (en) * 2011-06-09 2012-12-13 Biofuels Wales Limited Treatment of lignocellulosic material
EP3632534A4 (de) * 2017-05-23 2021-01-20 Microwave Chemical Co., Ltd. Verarbeitungseinheit

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2012000591A (es) * 2009-07-13 2012-06-01 Beta Renewables Spa Procedimiento para la separacion de lignina a alta temperatura.
JP5769165B2 (ja) * 2010-04-01 2015-08-26 国立大学法人 宮崎大学 セルロース系物質の分解方法
JP2011224499A (ja) * 2010-04-21 2011-11-10 Toyota Central R&D Labs Inc 糖又はその誘導体の製造方法
US10457930B2 (en) 2010-06-30 2019-10-29 Microwave Chemical Co., Ltd. Oil-based material-producing method and oil-based material-producing apparatus
US11224852B2 (en) 2011-06-29 2022-01-18 Microwave Chemical Co., Ltd. Chemical reaction apparatus and chemical reaction method
ITBO20110413A1 (it) 2011-07-11 2013-01-12 Spal Automotive Srl Macchina elettrica rotante e relativo metodo di assemblaggio.
JP5109004B1 (ja) * 2011-11-11 2012-12-26 マイクロ波化学株式会社 化学反応装置
JP5114616B1 (ja) 2011-11-11 2013-01-09 マイクロ波化学株式会社 化学反応装置
US11229895B2 (en) 2011-11-11 2022-01-25 Microwave Chemical Co., Ltd. Chemical reaction method using chemical reaction apparatus
JP5901247B2 (ja) * 2011-11-23 2016-04-06 マイクロ波化学株式会社 化学反応装置
US9078393B1 (en) 2012-03-13 2015-07-14 Activation Technologies, LLC Activated-release fertilizer, pesticides, and other granules, germination-activated seeds, and methods of making and using same
JP5909594B2 (ja) 2013-10-07 2016-04-26 第一高周波工業株式会社 強磁性体微粒子製造装置
JP2015089884A (ja) * 2013-11-06 2015-05-11 国立大学法人京都大学 リグニンモノマーの製造方法
GB2533820A (en) * 2015-01-05 2016-07-06 Arcs Energy Ltd A fuel activation and energy release apparatus, system and method thereof
JP6544596B2 (ja) * 2016-02-15 2019-07-17 国立大学法人京都大学 フェノール誘導体の製造方法
JP6945826B2 (ja) * 2016-09-09 2021-10-06 国立大学法人京都大学 セルロース及びヘミセルロースを含む組成物を製造する方法、並びにその組成物を用いて糖化を行う方法
CN109007543A (zh) * 2018-07-20 2018-12-18 育生（厦门）生物科技有限公司 降低含醣植物加工产品中5-羟甲基糠醛含量的方法

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3263052A (en) * 1963-09-11 1966-07-26 Cryodry Corp Power distribution system for microwave process chambers
US3535482A (en) * 1968-06-26 1970-10-20 Hammtronics Systems Inc Microwave apparatus for rapid heating of fluids
US3673370A (en) * 1970-04-03 1972-06-27 Cryodry Corp Microwave applicator system with cylindrical resonant cavity
JPS643119Y2 (de) * 1980-10-07 1989-01-26
FR2552125B1 (fr) 1983-09-16 1986-03-21 Interox Procede pour le taitement des matieres cellulosiques par des agents oxydants
JPS6119098A (ja) 1984-07-05 1986-01-27 日本化学機械製造株式会社 マイクロ波による連続加熱装置
US4714812A (en) * 1985-05-08 1987-12-22 John F. Woodhead, III Apparatus and method for processing dielectric materials with microwave energy
FR2599924B1 (fr) * 1986-06-06 1988-09-09 Univ Bordeaux 1 Dispositif modulaire pour l'application de micro-ondes en vue notamment du chauffage, sechage ou torrefaction d'un materiau
EP0287760A1 (de) * 1987-04-15 1988-10-26 HERMANN BERSTORFF Maschinenbau GmbH Vorrichtung zum gleichmässigen und schnellen Erwärmen, Pasteurisieren oder Sterilisieren von Lebensmitteln oder dergleichen
JPH02209901A (ja) * 1989-02-10 1990-08-21 Oji Paper Co Ltd マイクロ波処理によるリグノセルロース材料溶液の製造方法
FR2660147A1 (fr) * 1990-03-20 1991-09-27 Transitube Sa Installation pour proceder en continu au sechage, a la deshydratation ou a la cuisson par micro-ondes de produits granuleux ou pulverulents.
DK0626871T3 (da) * 1992-01-30 1997-10-27 Emery Microwave Management Inc Metode og apparat til kontrolleret reduktion af organisk materiale.
JP3478335B2 (ja) 1992-06-10 2003-12-15 三菱瓦斯化学株式会社 製紙用パルプの漂白方法
US6273955B1 (en) * 1995-08-28 2001-08-14 Canon Kabushiki Kaisha Film forming apparatus
DE69726320T2 (de) 1997-08-14 2004-10-21 Takashi Watanabe Chemisches verfahren zur depolymerisation von lignin
JP3839940B2 (ja) * 1997-11-26 2006-11-01 株式会社エス・ディー・エス バイオテック 含金属処理剤による木材の処理方法およびその方法により処理された木材
JP4636663B2 (ja) 2000-10-11 2011-02-23 四国計測工業株式会社 高温高圧容器への化学反応促進用マイクロ波供給装置
ATE381876T1 (de) * 2001-06-01 2008-01-15 Comm And Power Ind Inc Mikrowellenapplikator zur erwärmung einer strömenden flüssigkeit
JP2004285531A (ja) 2003-03-25 2004-10-14 Nippon Paper Industries Co Ltd 化学パルプの蒸解方法
JP2005268624A (ja) * 2004-03-19 2005-09-29 Sumitomo Osaka Cement Co Ltd 加熱装置
KR100894374B1 (ko) * 2004-07-27 2009-04-22 아사히 가세이 케미칼즈 가부시키가이샤 셀로올리고당의 제조 방법
JP2006088136A (ja) 2004-09-24 2006-04-06 Katsutoshi Okubo バイオマスエタノール生成物とバイオマスエタノール生成物製造方法
JP2006149343A (ja) 2004-11-26 2006-06-15 Daitoo Fujitekku:Kk 木質系バイオマスからのグルコース生成物とグルコース生成物製造方法
US20060231207A1 (en) * 2005-03-31 2006-10-19 Rebinsky Douglas A System and method for surface treatment
CN100365099C (zh) * 2006-02-27 2008-01-30 淮北市辉克药业有限公司 全新的生物质生产液体燃料技术
JP5461758B2 (ja) 2006-06-07 2014-04-02 四国計測工業株式会社 マイクロ波化学反応容器および装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010013696A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012168681A1 (en) * 2011-06-09 2012-12-13 Biofuels Wales Limited Treatment of lignocellulosic material
EP3632534A4 (de) * 2017-05-23 2021-01-20 Microwave Chemical Co., Ltd. Verarbeitungseinheit
US11633709B2 (en) 2017-05-23 2023-04-25 Microwave Chemical Co., Ltd. Treatment apparatus

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WO2010013696A1 (ja) 2010-02-04
CA2739056A1 (en) 2010-02-04
JP2014024850A (ja) 2014-02-06
JP5433870B2 (ja) 2014-03-05
EP2323461B1 (de) 2018-07-18
US20110263843A1 (en) 2011-10-27
EP2323461A4 (de) 2016-01-27
KR20110073432A (ko) 2011-06-29
KR101603362B1 (ko) 2016-03-14
JP5757012B2 (ja) 2015-07-29

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